EP2288426B1 - Katalytische zusammensetzungen bestehend aus zirkonium-, cer- und yttriumoxiden und ihre verwendung zur behandlung von abgasen. - Google Patents

Katalytische zusammensetzungen bestehend aus zirkonium-, cer- und yttriumoxiden und ihre verwendung zur behandlung von abgasen. Download PDF

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EP2288426B1
EP2288426B1 EP09735495.5A EP09735495A EP2288426B1 EP 2288426 B1 EP2288426 B1 EP 2288426B1 EP 09735495 A EP09735495 A EP 09735495A EP 2288426 B1 EP2288426 B1 EP 2288426B1
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Prior art keywords
oxide
cerium
yttrium
proportion
rare earth
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French (fr)
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EP2288426A2 (de
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Olivier Larcher
Emmanuel Rohart
Simon Ifrah
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Rhodia Operations SAS
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Rhodia Operations SAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/407—Zr-Ce mixed oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9207—Specific surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C01P2006/13—Surface area thermal stability thereof at high temperatures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a composition based on zirconium, cerium, yttrium and another rare earth oxides, its preparation methods and its use in catalysis, in particular for the treatment of automobile exhaust gases. .
  • multifunctional catalysts are used for the treatment of exhaust gases from internal combustion engines (automotive post-combustion catalysis).
  • Multifunctional means the catalysts capable of carrying out not only the oxidation in particular of carbon monoxide and of the hydrocarbons present in the exhaust gases but also the reduction in particular of the nitrogen oxides also present in these gases (catalysts "three ways").
  • Zirconium oxide and cerium oxide appear today as two particularly important and interesting constituents for this type of catalyst. More specifically, a quality required for these oxides or constituents is their reducibility.
  • reducibility is meant, here and for the rest of the description, the level of cerium IV in these constituents capable of transforming into cerium III under the effect of a reducing atmosphere and at a given temperature. This reducibility can be measured for example by consumption of hydrogen in a given temperature range. It is due to the cerium which has the property of reducing or oxidizing. This reducibility must, of course, be as high as possible.
  • this reducibility is stable, that is to say that it retains a value high enough for the products to remain effective even after exposure thereof to high temperatures.
  • JP 2000 176 282 describes a composition based on cerium, zirconium and yttrium oxides which does not include a rare earth chosen from lanthanum, neodymium and praseodymium.
  • US 2008/0090723 describes a composition based on cerium, zirconium and yttrium oxides but does not describe a specific surface of at least 40 m 2 / g after calcination at 1000 ° C. for 4 hours.
  • An object of the invention is therefore the development of a composition which can meet this need.
  • composition of the invention is as described in claim 1.
  • compositions of the invention have a significant reducibility at 1000 ° C. which can in particular be at least 90%.
  • specific surface is understood to mean the BET specific surface area determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 established on the basis of the method BRUNAUER - EMMETT- TELLER described in the periodical "The Journal of the American Chemical Society, 60, 309 (1938 ). "
  • the calcinations after which the surface values are given are calcinations in air.
  • Cerium oxide is in the form of ceric oxide, the oxides of the other rare earths in the form Ln 2 O 3 , Ln denoting the rare earth, with the exception of praseodymium expressed in the form Pr 6 O 11 .
  • compositions according to the invention are characterized first of all by the nature of their constituents.
  • compositions of the invention comprise at least one oxide of another rare earth which may be lanthanum, neodymium or praseodymium. It will be noted here that the combinations of these rare earths between them are of course included in the invention. Mention may be made more particularly of the combination of lanthanum and neodymium. The following description will be made for convenience with reference to a rare earth but this description should be understood as also applying to the combinations of the aforementioned rare earths.
  • compositions of the invention are also characterized by their contents of these different oxides. More specifically, they are characterized by a fairly low content of cerium oxide since it is between 3% and 15%. A content of cerium oxide higher than 15% can cause a reduction in the reducibility, a lower content can harm the catalytic properties of the compositions.
  • the content of yttrium oxide depends on the content of cerium oxide. Overall, this yttrium oxide content is lower the higher the cerium oxide content. This also applies to the total content of yttrium and rare earth oxides.
  • the maximum contents of yttrium oxide or of oxides of yttrium and of the other rare earth have been given above and their exceeding may, here again, cause a reduction in the reducibility of the compositions.
  • the minimum content of yttrium oxide is at least 3%, more particularly at least 5%.
  • the minimum content of other rare earth is at least 1%, preferably at least 2% in the case of neodymium and praseodymium.
  • compositions of the invention advantageously have a high reducibility rate.
  • This reducibility rate can be at least 90%. It can more particularly be at least 94%. Rates of 100% can be achieved.
  • the degree of reducibility given here is measured on a composition which has undergone calcination at 1000 ° C. in air for 4 hours in level.
  • the reducibility of the compositions is determined by measuring their hydrogen consumption measured between 100 ° C and 800 ° C. This measurement is made by programmed reduction in temperature using hydrogen diluted in argon and under conditions which will be specified later.
  • the reducibility rate represents the percentage of reduced cerium, it being understood that 1/2 mole of H 2 consumed and measured by this method corresponds to 1 mole of reduced CelV.
  • the reducibility properties of the compositions of the invention are also advantageous in that these compositions have a maximum reducibility temperature which can be quite low, in particular at most 550 ° C., more particularly at most 530 ° C.
  • This temperature is given here for compositions which have also been calcined at 1000 ° C. for 4 hours.
  • This maximum temperature corresponds to the temperature at which the hydrogen uptake is maximum and where, in other words, the reduction of cerium IV to cerium III is also maximum. It actually reflects the temperature at which the reducibility and, consequently, the effectiveness of the composition, are maximum.
  • the compositions are therefore effective in temperature ranges generally lower than those of known products for which this maximum temperature is often greater than 550 ° C.
  • the maximum reducibility temperature is also determined by measuring the hydrogen capture capacity as a function of the temperature. This temperature corresponds to the temperature at which the hydrogen uptake is maximum and where, in other words, the reduction of cerium IV to cerium III is also maximum.
  • compositions of the invention also have significant specific surfaces even after calcination at high temperature.
  • compositions have a specific surface after calcination for 4 hours at 1000 ° C. of at least 40 m 2 / g, preferably of at least 45 m 2 / g and even more preferably of at least 50 m 2 / g. Surface values of up to around 60 m 2 / g can be reached.
  • compositions of the invention may have a surface of at least 20 m 2 / g, in particular of at least 25 m 2 / g, more particularly of at least 30 m 2 / g.
  • the specific surfaces of the compositions of the invention can be at least 2 m 2 / g, more particularly at least 4 m 2 / g even more particularly at least 5 m 2 / g.
  • compositions of the invention have specific crystallographic properties.
  • the compositions of the invention have a majority phase of cubic or quadratic symmetry.
  • no characteristic peak of isolated rare earth oxide is observed, which reflects the incorporation of rare earth elements other than cerium in the crystalline matrix of the mixed oxide. .
  • compositions of the invention can be in the form of pure solid solutions of the elements cerium, yttrium and rare earth in zirconium oxide.
  • the X-ray diffraction diagrams of these compositions reveal the existence of a single phase and corresponding to that of a zirconium oxide crystallized in the cubic or quadratic system, thus translating the incorporation of the elements cerium, yttrium and rare earth in the crystal lattice of zirconium oxide, and therefore obtaining a true solid solution.
  • the high yttrium contents generally favor the appearance of the cubic phase.
  • solid solution is applicable to compositions which have undergone calcination at a temperature as high as 1100 ° C and for 4 hours. This means that after calcination under these conditions, no demixing is observed, that is to say the appearance of other phases.
  • compositions of the invention can be in the form of particles which have a concentration gradient of the yttrium and, optionally of the rare earth for the compositions containing one.
  • the particles have zones enriched in yttrium and, possibly, in other rare earth.
  • Step (a) is carried out in a liquid medium which is preferably water.
  • the compounds of zirconium, cerium, yttrium and the other rare earth are preferably soluble compounds. They may in particular be salts of these elements. These compounds can be chosen from nitrates, sulfates, acetates, chlorides, cerium-ammoniacal nitrate.
  • zirconium sulfate zirconyl nitrate or zirconyl chloride.
  • Zirconyl nitrate is most commonly used.
  • ceric nitrate is used. It is advantageous to use salts with a purity of at least 99.5% and more particularly of at least 99.9%.
  • An aqueous solution of ceric nitrate can for example be obtained by reaction of nitric acid with a hydrated ceric oxide prepared in a conventional manner by reaction of a solution of a cerous salt, for example cerous nitrate, and an ammonia solution in the presence of hydrogen peroxide.
  • oxidizing agent for example hydrogen peroxide
  • This oxidizing agent can be used by being added to the reaction medium during step (a), in particular at the end of the latter.
  • a soil as a starting compound for zirconium or cerium.
  • soil any system consisting of fine solid particles of colloidal dimensions, that is to say dimensions of between approximately 1 nm and approximately 500 nm, based on a zirconium or cerium compound, this compound generally being an oxide and / or a hydrated zirconium or cerium oxide, suspended in an aqueous liquid phase, said particles possibly also containing, optionally, residual amounts of bound or adsorbed ions such as, for example, nitrates, acetates, chlorides or ammoniums .
  • the zirconium or the cerium can be found either completely in the form of colloids, or simultaneously in the form of ions and in the form of colloids.
  • products of the hydroxide type can be used. Mention may be made of alkali or alkaline-earth hydroxides. It is also possible to use secondary, tertiary or quaternary amines. However, amines and ammonia may be preferred insofar as they reduce the risks of pollution by alkaline or alkaline earth cations. Mention may also be made of urea.
  • the basic compound can more particularly be used in the form of a solution.
  • Step (a) can be carried out using compounds initially in the solid state which are subsequently introduced into a base of the water tank for example, or even directly from solutions of these compounds and then mixing , in any order, of said solutions.
  • the contact between the compounds of zirconium, cerium, yttrium and the other rare earth and the basic compound can be carried out in any manner, for example by the addition of a mixture previously formed of the compounds of the above in the basic compound as a solution.
  • This variant is preferable for obtaining the compositions of the invention in the form of a pure cubic phase.
  • This bet in the presence is preferably carried out with stirring. It is preferably carried out at room temperature.
  • step (a) is carried out in two stages.
  • the compound of yttrium and / or that of the other rare earth can be used in the preparation process and participate in the reaction in a second step with respect to the zirconium and cerium compounds.
  • This variant makes it possible to obtain more particularly compositions according to the particular embodiment described above, that is to say those which have a concentration gradient of yttrium and, optionally rare earth.
  • the zirconium and cerium compounds and a part of the basic compound or all of it are brought into contact. It is also possible to use a yttrium compound or a rare earth compound here.
  • a second step the other part of said basic compound is brought into contact with the medium obtained at the end of the first step if it has not been used completely previously and the yttrium compound.
  • the yttrium and other rare earth compounds are used in this second step if none of them was used in the first step of step (a) or that of these two compounds which n 'was not implemented previously during the first stage of step (a).
  • step (a) At the end of step (a), a precipitate in suspension in the reaction medium is obtained.
  • the next step (b) of the process is the step of heating this precipitate in this medium.
  • This heating can be carried out directly on the reaction medium obtained after reaction with the basic compound or on a suspension obtained after separation of the precipitate from the reaction medium, optional washing and return to water of the precipitate.
  • the temperature to which the medium is heated is at least 100 ° C. and even more particularly at least 130 ° C. It can be for example between 100 ° C and 160 ° C.
  • the heating operation can be carried out by introducing the liquid medium into a closed enclosure (closed reactor of the autoclave type). Under the temperature conditions given above, and in an aqueous medium, it can thus be specified, by way of illustration, that the pressure in the closed reactor can vary between a value greater than 1 Bar (10 5 Pa) and 165 Bar (1 , 65. 10 7 Pa), preferably between 5 Bar (5 ⁇ 10 5 Pa) and 165 Bar (1.65. 10 7 Pa). Heating can also be carried out in an open reactor for temperatures close to 100 ° C.
  • the heating can be carried out either in air or in an inert gas atmosphere, preferably nitrogen.
  • the duration of the heating can vary within wide limits, for example between 1 and 48 hours, preferably between 2 and 24 hours.
  • the temperature rise takes place at a speed which is not critical, and the fixed reaction temperature can thus be reached by heating the medium, for example between 30 minutes and 4 hours, these values being given entirely indicative fact.
  • the precipitate obtained after the heating step and possibly washing can be resuspended in water and then another heating of the medium thus obtained. This other heating is done under the same conditions as those which were described for the first.
  • the next step (c) of the process consists in adding to the precipitate from the previous step an additive which is chosen from anionic surfactants, nonionic surfactants, polyethylene glycols and carboxylic acids and their salts as well as surfactants of the carboxymethylated fatty alcohol ethoxylates type.
  • anionic type surfactants ethoxycarboxylates, ethoxylated fatty acids, sarcosinates, phosphate esters, sulfates such as alcohol sulfates, ether alcohol sulfates and alkanolamide ethoxylates sulfates, sulfonates such as sulfosuccinates, may be mentioned.
  • alkyl benzene or alkyl naphthalene sulfonates alkyl benzene or alkyl naphthalene sulfonates.
  • carboxylic acids it is possible in particular to use the aliphatic mono- or dicarboxylic acids and, among these, more particularly the saturated acids. It is also possible to use fatty acids and more particularly saturated fatty acids. We can cite in particular formic, acetic, propionic, butyric, isobutyric, valeric, caproic, caprylic, capric, lauric, myristic, palmitic acids.
  • dicarboxylic acids there may be mentioned oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acids.
  • the salts of the carboxylic acids can also be used, in particular the ammoniacal salts.
  • lauric acid and ammonium laurate there may be mentioned more particularly lauric acid and ammonium laurate.
  • product of the carboxymethylated fatty alcohol ethoxylate type is meant the products consisting of ethoxylated or propoxylated fatty alcohols comprising at the chain end a CH 2 -COOH group.
  • R 1 -O- (CR 2 R 3 -CR 4 R 5 -O) n -CH 2 -COOH in which R 1 denotes a carbon chain, saturated or unsaturated, the length of which is generally at most 22 carbon atoms, preferably at least 12 carbon atoms; R 2 , R 3 , R 4 and R 5 may be identical and represent hydrogen or alternatively R 2 may represent a CH 3 group and R 3 , R 4 and R 5 represent hydrogen; n is a non-zero integer up to 50 and more particularly between 5 and 15, these values being included.
  • a surfactant can consist of a mixture of products of the above formula for which R 1 can be saturated and unsaturated respectively or else products comprising both groups -CH 2 -CH 2 - O- and -C (CH 3 ) -CH 2 -O-.
  • the addition of the surfactant can be done in two ways. It can be added directly to the precipitate suspension from the previous heating step (b). It can also be added to the solid precipitate after separation from the latter by any known means from the medium in which the heating took place.
  • the amount of surfactant used is generally between 5% and 100%, more particularly between 15% and 60%.
  • the precipitate is washed after having separated it from the medium in which it was found. suspension.
  • This washing can be done with water, preferably with water at basic pH, for example ammonia water.
  • the precipitate recovered is then calcined.
  • This calcination makes it possible to develop the crystallinity of the product formed and it can also be adjusted and / or chosen as a function of the subsequent temperature of use reserved for the composition according to the invention, and this taking into account the fact that the specific surface of the The lower the calcination temperature used, the lower the product.
  • Such calcination is generally carried out in air, but calcination carried out for example under inert gas or under a controlled atmosphere (oxidizing or reducing) is obviously not excluded.
  • the calcination temperature is generally limited to a range of values between 500 and 1000 ° C.
  • compositions according to the particular embodiment described above that is to say those which have a concentration gradient of yttrium and, optionally rare earth .
  • This process differs from the process according to the first mode essentially by the way in which the yttrium and the rare earth are introduced.
  • only part of the yttrium and / or rare earth compounds is used in the first step (a ') and not all of them as well as the basic compound which is used here either in whole or in part only.
  • the rest is then introduced at the end of the heating step (b ') to precipitate the remaining part of the yttrium and / or rare earth compounds.
  • the remaining amount of the basic compound is also introduced at this time if it has not been used in full in step (a ').
  • step (c') Depending on the composition which one aims to prepare and the desired characteristics, it is perfectly possible to modulate the order of introduction of the compounds, for example introducing all of the yttrium compound and only partially of that of the rare earth in step (a ') or vice versa or even a part of the two compounds and the rest in step (c').
  • the invention also covers a composition which has the proportions of oxides of these different elements given above and which is capable of being obtained by the process comprising the steps (a ') (b') (c ') ( d ') and (e') which have been described above.
  • compositions of the invention as described above or as obtained by the methods studied above are in the form of powders but they can optionally be shaped to be in the form of granules, beads, cylinders or nests. bee of variable dimensions.
  • compositions of the invention can be used as catalysts or catalyst supports.
  • the invention also relates to catalytic systems comprising the compositions of the invention.
  • these compositions can thus be applied to any support usually used in the field of catalysis, that is to say in particular thermally inert supports.
  • This support can be chosen from alumina, titanium oxide, cerium oxide, zirconium oxide, silica, spinels, zeolites, silicates, crystalline silicoaluminum phosphates, phosphates crystalline aluminum.
  • compositions can also be used in catalytic systems comprising a coating (wash coat) with catalytic properties and based on these compositions, on a substrate of the type, for example metallic or ceramic monolith.
  • the coating may also include a support of the type of those mentioned above. This coating is obtained by mixing the composition with the support so as to form a suspension which can then be deposited on the substrate.
  • catalytic systems and more particularly the compositions of the invention can find numerous applications. They are thus particularly well suited to, and therefore usable in the catalysis of various reactions such as, for example, dehydration, hydrosulfurization, hydrodenitrification, desulfurization, hydrodesulfurization, dehydrohalogenation, reforming, reforming to steam, cracking, hydrocracking, hydrogenation, dehydrogenation, isomerization, disproportionation, oxychlorination, dehydrocyclization of hydrocarbons or other organic compounds, oxidation and / or reduction reactions, Claus reaction, the treatment of exhaust gases from internal combustion engines, demetallation, methanation, shift conversion, catalytic oxidation of soot emitted by internal combustion engines such as diesel or petrol engines operating under lean conditions .
  • the catalytic systems and the compositions of the invention can finally be used as NOx traps or to promote the reduction of NOx even in an oxidizing medium.
  • the compositions of the invention are used in combination with precious metals, they thus play the role of support for these metals.
  • the nature of these metals and the techniques for incorporating them into the support compositions are well known to those skilled in the art.
  • the metals can be platinum, rhodium, palladium or iridium, they can in particular be incorporated into the compositions by impregnation.
  • the invention also relates to a method of treating exhaust gases from internal combustion engines which is characterized in that a catalyst system as described above or a composition according to l is used as catalyst. invention and as previously described.
  • the measurement of the reducibility rate is made under the following conditions.
  • the reducibility rate of cerium is measured by performing a programmed temperature reduction on a Micromeritics Autochem II device. This the device makes it possible to measure the hydrogen consumption of a composition according to the invention as a function of the temperature and to deduce therefrom the reduction rate of cerium.
  • thermocouple placed at the level of the sample.
  • the hydrogen consumption during the reduction phase is deduced by calibrating the variation of the thermal conductivity of the gas flow measured at the outlet of the cell using a thermal conductivity detector (TCD).
  • TCD thermal conductivity detector
  • the reduction rate of cerium is calculated from the hydrogen consumption measured between 100 ° C and 800 ° C.
  • This example relates to a composition with 83% of zirconium, 5% of cerium, 2% of lanthanum 5% of yttrium and 5% of neodymium, these proportions being expressed in percentages by mass of the oxides ZrO 2 , CeO 2 , La 2 O 3 , Y 2 O 3 and Nd 2 O 3 .
  • 313 ml of zirconium nitrate (266 g / l as ZrO 2 ), 19.7 ml of cerium nitrate, 4.4 ml of lanthanum nitrate (456 g / l as La 2 O 3 ), 13.1 ml are introduced into a stirred beaker yttrium nitrate (382 g / l as Y 2 O 3 ) and 9.5 ml of neodymium nitrate (524 g / l as Nd 2 O 3 ). It is then made up with distilled water so as to obtain 1 liter of a nitrate solution.
  • the nitrate solution is introduced into the reactor with constant stirring.
  • the solution obtained is placed in a stainless steel autoclave equipped with a stirring mobile.
  • the temperature of the medium is brought to 150 ° C. for 2 hours with stirring.
  • the suspension is then filtered through Büchner, then ammonia water is added to the filtered precipitate at the rate of once the volume of the filtration mother liquors.
  • the product obtained is then brought to 700 ° C for 4 hours in level.
  • Example 8 we start with a dilute solution B containing neodymium nitrate and a dilute solution A containing all of the other constituents.
  • Solution B is added to the ammonia solution after solution A and then the whole is heated as in Example 1.
  • solution B contains yttrium nitrate.
  • solution B contains yttrium nitrate and neodymium nitrate.
  • the praseodymium nitrate solution has a concentration of 500 g / l of Pr 6 O 11 .
  • Table 1 The volumes of different reagent solutions used for the preparation of the compositions of the examples are shown in Table 1 below.
  • Table 2 gives the oxide contents of different compositions obtained at the end of these preparations.
  • Table 3 indicates the surface values of these same compositions and Table 4 their reducibility properties after calcination at 1000 ° C for 4 hours.
  • the reducibility profiles established during the measurement of the reducibility rate according to the method given above for these oxides show peaks at low temperature, which means that these oxides have a fraction of cerium reducible at low temperature.
  • the temperature at which this first reduction takes place is between 150 and 230 ° C.
  • the area corresponding to this peak is equivalent to between 3 and 15% of the total area under the reducibility curve. This means that the fraction of cerium reducible at low temperature represents between 3 and 15% of the total cerium when the reducibility is 100%.
  • compositions of the invention begin to exhibit redox properties from low temperatures, in particular in a temperature range between 150 ° C and 230 ° C.
  • Table 1 Quantities of reagents used expressed in volume (ml) of the solutions of the salts of the different elements
  • Example V Zr V Ce V La VY V Nd V Pr V ammonia 1 313 19.7 4.4 13.1 9.5 - 203 2 275 19.7 4.4 13.1 28.6 - 204 3 256 19.7 4.4 52.4 9.5 - 221 4 218 19.7 4.4 52.4 28.6 - 222 5 266 19.7 4.4 32.4 19.1 - 212 6 301 19.7 - 26.2 - 10.0 208 7 294 39.4 4.4 13.1 9.5 - 208 8 282 39.4 4.4 20.9 9.5 - 211 9 313 39.4 - 18.3 - - 209 10 271 39.4 - 20.9 19.1 - 212 11 256 39.4 4.4 13.1 28.
  • Example 9 is not part of the invention.
  • Table 3 Specific areas in m 2 / g
  • Example 13 Two oxides of composition ZrO 2 / CeO 2 / Y 2 O 3 / Nd 2 O 3 are prepared 75/10/5/10.
  • Example 13 is carried out according to the procedure of Example 1.
  • the starting point is a dilute solution B containing neodymium and yttrium nitrates and a dilute solution A containing all of the other constituents.
  • Solution B is added to the ammonia solution after solution A and the whole is heated as in Example 1.
  • a dilute nitric acid leaching test makes it possible to compare the yttrium content at the surface of the oxides prepared according to these two methods. This test is carried out as follows: 1 gram of oxide is dispersed with stirring in 10 ml of a solution containing 0.1 mol / l of nitric acid. After stirring for 2 hours at 40 ° C, the suspension is filtered. Analysis of the filtrate by ICP technique makes it possible to determine the quantities of yttrium recovered. To determine the yttrium fractions recovered, these values are divided respectively by the amount of yttrium present in the oxide test sample. The results obtained for Examples 13 and 14 are presented in Table 5 below: Table 5 Yttrium fraction recovered (%) Example 14 5 Example 15 19
  • an X-ray diffraction analysis is carried out.
  • the analyzes are carried out on powder using a Panalytical diffractometer equipped with a multi-channel detector of the X'Celerator type and a K ⁇ / K ⁇ monochromator.

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Claims (5)

  1. Zusammensetzung, bestehend aus Oxiden von Zirconium, Cer, Yttrium und mindestens einem Oxid eines Seltenerdmetalls, das aus Lanthan, Neodym und Praseodym ausgewählt ist, gekennzeichnet durch die folgenden Gewichtsanteile dieser Oxide:
    ▪ der Anteil an Ceroxid liegt zwischen 3 % und 15 %;
    ▪ der Anteil an Yttriumoxid beträgt mindestens 3 % und
    ▪ höchstens 6 %, wenn der Anteil an Ceroxid zwischen 12 % exklusive und 15 % inklusive liegt;
    ▪ höchstens 10 %, wenn der Anteil an Ceroxid zwischen 7 % exklusive und 12 % inklusive liegt;
    ▪ höchstens 30 %, wenn der Anteil an Ceroxid zwischen 3 und 7 % inklusive liegt;
    ▪ wobei der Anteil an dem Oxid des Seltenerdmetalls, das aus Lanthan, Neodym und Praseodym ausgewählt ist, so definiert ist:
    ▪ er beträgt mindestens 1 %;
    ▪ er beträgt höchstens 10 %, wenn der Anteil an Ceroxid zwischen 12 % exklusive und 15 % inklusive liegt;
    ▪ er beträgt höchstens 18 %, wenn der Anteil an Ceroxid zwischen 7 % exklusive und 12 % inklusive liegt;
    ▪ der Gesamtanteil an Yttriumoxid und Oxid des Seltenerdmetalls, das aus Lanthan, Neodym und Praseodym ausgewählt ist, beträgt mehr als 30 %, wenn der Anteil an Ceroxid zwischen 3 % und 7 % inklusive liegt;
    ▪ Rest Zirconiumoxid;
    sowie durch eine spezifische Oberfläche von mindestens 40 m2/g nach 4 Stunden Calcinierung bei 1000 °C;
    wobei die Zusammensetzung eine Hauptphase mit kubischer oder quadratischer Symmetrie aufweist oder auch in Form einer reinen festen Lösung der Elemente Cer, Yttrium und Seltenerdmetall in dem Zirconiumoxid vorliegt.
  2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass der Yttriumgehalt mindestens 5 % beträgt, wobei dieser Gehalt als Oxidmasse angegeben ist.
  3. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass er nach 4 Stunden Calcinierung bei 1100 °C eine spezifische Oberfläche von mindestens 20 m2/g aufweist.
  4. Katalytisches System, dadurch gekennzeichnet, dass es eine Beschichtung (Washcoat) mit katalytischen Eigenschaften auf der Basis einer Zusammensetzung nach einem der Ansprüche 1 bis 3 auf einem Substrat vom Typ Metall- oder Keramik-Monolith umfasst.
  5. Verfahren zur Behandlung von Abgasen von Verbrennungsmotoren, dadurch gekennzeichnet, dass man als Katalysator ein katalytisches System nach Anspruch 4 oder eine Zusammensetzung nach einem der Ansprüche 1 bis 3 verwendet.
EP09735495.5A 2008-04-23 2009-04-21 Katalytische zusammensetzungen bestehend aus zirkonium-, cer- und yttriumoxiden und ihre verwendung zur behandlung von abgasen. Active EP2288426B1 (de)

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PCT/EP2009/054715 WO2009130202A2 (fr) 2008-04-23 2009-04-21 Composition a base d'oxydes de zirconium, de cerium et d'yttrium, a reductibilite elevee, procedes de preparation et utilisation en catalyse

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JP5883425B2 (ja) * 2013-10-04 2016-03-15 株式会社豊田中央研究所 セリア−ジルコニア系複合酸化物及びその製造方法、並びにそのセリア−ジルコニア系複合酸化物を用いた排ガス浄化用触媒
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CN103962120A (zh) 2014-08-06
KR20100139064A (ko) 2010-12-31
FR2930456A1 (fr) 2009-10-30
US20150202596A1 (en) 2015-07-23
CA2725431C (fr) 2018-01-16
DK2288426T3 (da) 2020-05-04
US20110206583A1 (en) 2011-08-25
CN102015069A (zh) 2011-04-13
WO2009130202A3 (fr) 2009-12-23
JP5647974B2 (ja) 2015-01-07
RU2468855C2 (ru) 2012-12-10
EP2288426A2 (de) 2011-03-02
RU2010147649A (ru) 2012-05-27
CA2725431A1 (fr) 2009-10-29
KR101316986B1 (ko) 2013-10-15
US10350578B2 (en) 2019-07-16
JP2011520745A (ja) 2011-07-21
FR2930456B1 (fr) 2010-11-19
WO2009130202A2 (fr) 2009-10-29
PL2288426T3 (pl) 2020-09-07

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